JPH0155099B2 - - Google Patents

Abstract

Described herein are laminate compositions comprising a polyarylate, or blends thereof, derived from a dihydric phenol and an aromatic dicarboxylic acid which is laminated upon the surface of a poly(aryl ether), particularly polysulfone. In contrast to the highly ultraviolet sensitive polysulfone, the laminate compositions of this invention exhibit good weatherability including no adverse effects, e.g., degradation, from prolonged ultraviolet irradiation exposure. The laminate compositions of this invention have beneficial utility in solar energy applications.

Description

[Detailed description of the invention]

The present invention relates to a laminate in which a polyarylate derived from a dihydric phenol and an aromatic dicarboxylic acid or a mixture thereof is laminated on the surface of a poly(aryl ether), particularly a polysulfone. Polyarylates effectively protect poly(arylether) substrates from the deleterious effects of long-term exposure, including exposure to ultraviolet radiation, even in thin coatings or layers, such as 1.5 mils thick. Poly(aryl ethers) during long-term exposure, including exposure to this ultraviolet radiation.
Retention of desirable mechanical and chemical properties is achieved when the polyarylate is laminated onto the poly(arylether) surface. The laminate of the present invention is advantageously used to utilize solar energy. The present invention discloses a laminate in which a polyarylate derived from a dihydric phenol and an aromatic dicarboxylic acid or a mixture thereof is laminated on the surface of a poly(arylether), particularly a polysulfone. . Polyarylates mixed with certain thermoplastic polymers, such as those described in U.S. Pat. It is known that it exhibits good weather resistance. Similarly, poly(ethylene terephthalate), poly(vinyl chloride), polycarbonate, poly(methyl methacrylate), polystyrene, etc., as described in the prior art documents listed below.
It is also known that polyarylates coated or laminated onto certain thermoplastic polymers exhibit good weather resistance without apparent deleterious effects from long-term exposure to ultraviolet radiation. . However, when a polyarylate is mixed with a poly(arylether) thermoplastic polymer, especially polysulfone, and subjected to long-term exposure, including exposure to ultraviolet radiation, the mixture of the polyarylate and polysulfone after exposure is also known to exhibit deterioration of mechanical and chemical properties. Since polyarylate/polysulfone blends exhibit degradation of mechanical and chemical properties caused by exposure to UV radiation, polyarylate/polysulfone laminates are susceptible to UV radiation as illustrated in the Examples below. The excellent stability upon exposure is unexpected and non-obvious. Thermoplastic polymers of poly(aryl ether), especially polysulfone, are tough, stiff, and high-strength thermoplastics, with properties ranging from -150 to 300
Maintained over a wide temperature range up to In addition, 〓 is converted to °C using the following formula. C=(〓-32)×5/9 The polymer has a continuous use temperature of about 300℃.
The polymers are hydrolytically stable and have excellent mechanical, electrical and chemical properties, which makes them useful for forming various articles, preferably articles useful in heat transfer applications. be able to. For example, polysulfone can be preferably formed into radiation absorbing collector elements used in solar heaters. Polysulfone connects the radiation-absorbing collector element with the liquid or gaseous medium to be heated when the collector element is coupled to a mechanism for passing the gaseous or liquid medium to be heated through the housing of the solar heater. is highly desirable and effective in establishing an efficient heat transfer relationship between the solar heater and the solar heater housing. However, polysulfone itself is very sensitive to degradation resulting from long-term exposure to UV radiation. Therefore, it increases the resistance of polysulfone to deterioration resulting from exposure to long-term ultraviolet radiation, and makes polysulfone suitable for harnessing solar energy without substantially affecting its mechanical and chemical properties. It is desirable to be able to use it. polyarylate, poly(aryl ether),
It has been unexpectedly and non-obviously found as a result of the present invention that polysulfone provides excellent protection against degradation resulting from long-term exposure to ultraviolet radiation, particularly when laminated onto the surface of polysulfone. . Laminates comprising polyarylates laminated onto the surface of poly(aryl ethers), particularly polysulfones, are desirable for use in solar energy harvesting. of polysulfone during long-term exposure, including exposure to ultraviolet radiation.
Maintenance of desirable mechanical and chemical properties is also achieved when polyarylates are laminated onto the surface of the polysulfone. The following prior art documents describe aromatic polyarylates useful as UV light barriers, such as polyarylates derived from dihydric phenols and aromatic dicarboxylic acids. U.S. Pat. No. 3,444,129 discloses a rearrangement polymer which is a polymerization reaction product of an aromatic dihydrogen compound such as dihydric phenol and an aromatic dicarboxylic compound such as aromatic dicarboxylic acid. The aromatic polyester obtained is disclosed. The rearrangeable aromatic polyesters are useful as UV barriers. U.S. Pat. No. 3,460,961 describes a substrate protected by two adjacently stacked transparent aromatic polyester coatings. The aromatic polyester compound is a reaction product of an aromatic dihydrogen compound such as dihydric phenol and an aromatic dicarboxylic compound such as aromatic dicarboxylic acid. The aromatic polyester coating rearranges in the presence of ultraviolet light to produce a transparent compound that is stable to ultraviolet light and acts as a barrier. U.S. Patent No. 3,492,261 discloses a rearrangement reaction product which is a polymerization reaction product of an aromatic dihydrogen compound such as a dihydric phenol and an aromatic dicarboxylic compound such as an aromatic dicarboxylic acid. A film-forming solution of aromatic polyester that can be used is described. The aromatic polyester solution, which can be coated onto a substrate and then dried to form a transparent film, absorbs and translocates in the presence of ultraviolet light and is stable to ultraviolet light. , and can produce transparent compounds that act as barriers. US Pat. No. 3,503,779 discloses a rearrangement polymer which is a polymerization reaction product of an aromatic dihydrogen compound such as dihydric phenol and an aromatic dicarboxylic compound such as aromatic dicarboxylic acid. A substrate coated with an aromatic polyester is disclosed. The externally exposed surface of the aromatic polyester coating rearranges under the influence of ultraviolet light to produce a new transparent compound that is stable to ultraviolet light and acts as a barrier. U.S. Pat. No. 3,506,470 relates to photographic prints coated with an aromatic polyester solution, in which the thin film of the solution is transparent, and the thin film is stable to ultraviolet light by dislocation in the presence of ultraviolet light. , and produce a transparent compound that acts as a barrier. The aromatic polyester is a polymerization reaction product of an aromatic dihydrogen compound such as dihydric phenol and an aromatic dicarboxylic compound such as aromatic dicarboxylic acid. The patent specification states that coated photographic prints are protected from the harmful effects of ultraviolet light and retain their color and clarity for a longer period of time than uncoated photographic prints. Transparent Ultraviolet, SM Cohen, RH Young and AH Markhardt, Journal of Polymer Science, Part A-1, Volume 9, pp. 3263-3299 (1971).
In Barrier Coatings, useful as protective coatings for substrates normally sensitive to ultraviolet light, including polyarylates derived from dihydric phenols and aromatic dicarboxylic acids. The synthesis of a number of phenyl polyesters is described. The molecular skeleton of the phenyl polyester rearranges under UV radiation to form an o-hydroxybenzophenone structure. This photochemical Fries rearrangement produces UV opacity in the exposed film while maintaining visual transparency. These phenyl polyesters,
A thin coating, for example 0.3 to 0.5 mils thick, protects the substrate, which is normally sensitive to ultraviolet light. Spectroscopic analysis of various rearranged films and coatings shows that the o-hydroxybenzophenone polymer formed is concentrated as a "skin" on the irradiated surface of the initial phenyl polyester coating. It will be done. The skin formed in situ during irradiation serves to protect both the initial phenyl polyester coating as well as the coated substrate from degradation due to UV radiation. The paper further describes the "healing" mechanism, in detail, when the exposed epidermis eventually deteriorates under long-term UV irradiation, a larger amount of the underlying polyester layer is clearly dislocated. It describes a mechanism for compensating for losses. That is, the transparent coating acts both as a protective skin and as a dislocatable reservoir. Although the use of a number of thermoplastic polymer substrates, such as poly(ethylene terephthalate), poly(vinyl chloride), polycarbonate, poly(methyl methacrylate), polystyrene, etc., has been demonstrated in each of the above prior art documents, With the exception of the aforementioned US Pat. No. 3,506,470, which concerns only photographic prints, the use of polysulfone thermoplastic polymer substrates is not described in any of these documents. As previously indicated, when polyarylates and polysulfones are mixed and the mixture is subjected to exposure, including exposure to ultraviolet radiation, a deterioration of the mechanical and chemical properties of the mixture is observed. . This is in contrast to other known polyarylate thermoplastic polymer blends, coatings and laminates mentioned above which exhibit good weathering properties that are not adversely affected by long-term exposure to UV radiation. It is therefore clear that poly(arylethers), especially polyarylates layered onto the surface of polysulfones, provide excellent protection for polysulfones against degradation resulting from long-term exposure, including exposure to ultraviolet radiation. It's unexpected. Moreover,
None of the above prior art documents discloses or suggests any beneficial use of the laminates of the present invention in harnessing solar energy. A laminate in which a polyarylate derived from a divalent phenol and an aromatic dicarboxylic acid or a mixture thereof is laminated on the surface of a poly(arylether), especially a polysulfone, and moreover, it can utilize solar energy. The present inventors are currently completely unaware of the above-mentioned prior art documents and prior art disclosing laminates having useful applications in the art. The present invention provides a laminate in which a polyarylate derived from a dihydric phenol and an aromatic dicarboxylic acid or a mixture thereof is laminated on the surface of a poly(arylether), particularly a polysulfone. Since polysulfone itself is very sensitive to degradation resulting from long-term exposure to UV radiation, the polyarylates are highly sensitive to UV radiation even in thin coatings or layers, such as 1.5 mils thick. Provides polysulfone with an excellent protective barrier from the adverse effects of long-term exposure, including exposure. Retention of desirable mechanical and chemical properties of polysulfones during long-term exposure, including exposure to ultraviolet radiation, is also achieved when polyarylates are laminated onto the surface of the polysulfones. The laminates of the present invention have beneficial applications in harnessing solar energy. radiation absorbing collector elements used for example in solar heaters.
absorbent collector element) can be preferably constituted by the laminate of the present invention. heating through the solar heater housing, when the collector element is coupled to a mechanism for passing a liquid or gaseous medium to be heated through the solar heater housing; In configuring the collector element to provide an effective heat transfer relationship with the mechanism for passing the liquid or gaseous medium to be
The laminate of the present invention is highly preferred and effective. As used herein, the term "laminate" refers to any coating, coating, lamination, etc., such as a polyarylate, on or over a substrate, such as a poly(arylether). , refers to articles that are arranged or stacked regardless of whether or not they are in contact with the base material. The polyarylates of the present invention are derived from dihydric phenols and at least one aromatic dicarboxylic acid. A particularly desirable divalent phenol has the following formula: [wherein Y is selected from an alkyl group having 1 to 4 carbon atoms, chlorine, or bromine, and each z
independently has a value from 0 to 4, R' is a divalent, saturated or unsaturated aliphatic hydrocarbon group, in particular an alkylene or alkylidene group having 1 to 3 carbon atoms, or a carbon atom a cycloalkylidene group or a cycloalkylene group having up to 9 atoms. A preferred dihydric phenol is bisphenol A. Other dihydric phenols useful in making the polyarylates of this invention include hydroquinone and resorcinol. The dihydric phenols can be used alone or in combination. Aromatic dicarboxylic acids that can be used in the present invention include terephthalic acid, isophthalic acid, any naphthalene dicarboxylic acids and mixtures thereof: as well as alkyl-substituted homologs of these carboxylic acids (in which case the alkyl group has 1 carbon atom and acids with other inert substituents, such as halides, alkyl ethers, or aryl ethers.
Preferably a mixture of isophthalic acid and terephthalic acid is used. The ratio of isophthalic acid to terephthalic acid in the mixture is from about 20:80 to about 100:0, with the most preferred acid ratio being from about 75:25 to about 25:75. Also, about 0.5 to about 20% of aliphatic diacids having from 2 to about 10 carbon atoms, such as adipic acid, sebacic acid, etc., can also be used in the polymerization reaction. The polyarylate of the present invention is a reaction between an acid chloride of an aromatic dicarboxylic acid and a divalent phenol; a reaction between a diaryl ester of an aromatic dicarboxylic acid and a divalent phenol; or a diester of an aromatic diacid and a divalent phenol. It can be made by any known prior art polyester forming reaction, such as reaction with derivatives. These methods are described, for example, in U.S. Pat.
It is described in specifications No. 3824213 and No. 3133898. The polyarylate used in the present invention is preferably produced by the method described in JP-A-57-87420. This published patent publication states that approximately 0.5 to
An improved method for producing polyarylates having a reduced viscosity of 1.0 dl/gm or higher is described,
The process comprises: (a) reacting an acid anhydride derived from an acid having 2 to 8 carbon atoms with at least one dihydric phenol to form the corresponding diester; (b) reacting the diester with at least one aromatic dicarboxylic acid at a temperature sufficient to form a polyarylate, wherein the improvement includes reducing residual anhydride after forming the dihydric phenolic diester. It consists of removing the acid and reducing its concentration to about 1500 ppm or less. The poly(arylether) resin component suitable for use in the present invention is a linear thermoplastic polyarylene polyether polysulfone in which arylene units are interspersed with ether and sulfone linkages. These resins can be obtained from the reaction of an alkali metal double salt of a divalent phenol and a dihalobenzenoid compound, and in this case, either or both of the alkali metal double salt and the dihalobenzenoid compound have arylene coordination. A sulfone bond or a ketone bond between, i.e. −SO ₂
- or -CO-, giving a sulfone or ketone unit in addition to an arylene unit and an ether unit in the polymer chain. The polysulfone polymer has the formula: (-O-E-O-E')- (where E is a residue of divalent phenol,
E′ is a residue of a benzenoid compound having an inert electron-withdrawing group in at least one of the positions ortho or para to the valence bond, and both residues are connected to an ether oxygen through an aromatic carbon atom. It has a basic structure that includes cyclic units of (valently bonded). Such polysulfones are included in the class of polyarylene polyether resins described, for example, in US Pat. Nos. 3,264,536 and 4,108,837. The residue E of divalent phenol has the structural formula: [In the formula, Ar is an aromatic group, preferably a phenylene group, and A and A ₁ are inert substituents which may be the same or different, and are an alkyl group having 1 to 4 carbon atoms. or a halogen atom, namely fluorine, chlorine, bromine or iodine, or an alkoxy group having 1 to 4 carbon atoms, r and r ₁ are integers having a value of 0 to 4, and R ₁ is dihydroxy Denotes a bond between aromatic carbon atoms as in diphenyl, or divalent groups including e.g. CO, O, S, S-S, _SO2 , or divalent groups such as alkylene, alkylidene, cycloalkylene, cycloalkylidene. organic hydrocarbon group, or halogen, alkyl,
aryl, substituted alkylene, alkylidene, cycloalkylene and cycloalkylidene groups and alkylene and aromatic groups, and a ring fused to both Ar. The divalent phenolic residue E is also derived from mononuclear phenols such as hydroquinone. A typically preferred polymer is disclosed in the above-mentioned U.S. Patent No.
The following structural formula as described in specification No. 4108837: It has a repeating unit of In the above, A and A ₁
can be the same or different, such as an alkyl group having 1 to 4 carbon atoms, a halogen atom (e.g. fluorine, chlorine, bromine or iodine) or an alkoxy group having 1 to 4 carbon atoms. is an inert substituent, and r and r ₁ are integers having a value of 0 to 4. Typically R ₁ represents a bond between aromatic carbon atoms or a divalent bonding group and R ₂ represents sulfone, carbonyl or sulfoxide. Preferably R ₁ represents a bond between aromatic carbon atoms. In the above formula, r and r ₁ are zero, and R ₁ is the formula: (In the formula, R'' is a lower alkyl group, an aryl group, or a halogen substituent thereof, preferably methyl), and a thermoplastic polysulfone in which R ₂ is a sulfone group is more preferred. The poly(aryl ether) has a reduced viscosity of about 0.4 to about 1.5 dl/g as measured in a suitable solvent at a temperature appropriate for the respective polyether, such as methylene chloride at 25°C. Preferred. Poly(aryl ether) has the following formula: as well as It has a repeating unit of Other additives can be included in the laminate of the present invention. These additives include plasticizers, pigments, flame retardant additives, especially triaryl phosphates such as decabromodiphenyl ether and triphenyl phosphate, heat stabilizers, UV stabilizers, processing aids, etc. . Of particular importance in the present invention are polymeric additives that produce transparent products when mixed with polyarylates. These polymeric additives include poly(ethylene terephthalate), poly(butylene terephthalate), polyesters based on cyclohexanedimethanol reacted with aromatic dicarboxylic acids, and polycarbonates. These additives provide the ability to moderate the viscosity of the polyarylate to match that of the polysulfone and improve coextrudability. Although the preferred laminate is transparent, it is also recognized within the scope of this invention that the polysulfone layer or both the polysulfone and polyarylate layers be colored. Polysulfone colored with carbon black exhibits good mechanical performance after exposure to UV radiation. However, some surface yoking does occur. Of course, coloring the radiation absorbing collector element or heat transfer conduit black makes the absorption of radiation more effective. The advantage of transparent laminates in harnessing solar energy is that the opacity of polysulfone in high frequency radiation, such as the infrared part of the spectrum, reduces radiation losses. Heat transfer conduits constructed from transparent laminates can therefore be used as radiation suppression devices often included in advanced solar energy harvesting. If transparent heat transfer conduits are used, the liquid medium, such as water, should be suitably treated to effectively absorb radiation. For example, water can be colored black. Polyarylates provide desirable protection for poly(aryl ether), especially polysulfone, substrates from the adverse effects of long-term exposure, including exposure to ultraviolet radiation, even in coatings or layers as thin as, for example, 1.5 mils thick. do. Preferably, the laminates of the present invention have a polyarylate layer thickness of at least about 1 mil, and most preferably at least about 2.5 mil. Since polyarylates have low scratch and abrasion resistance, the thickness of the polyarylate layer should be adjusted to ensure long-term protection against poly(arylethers), especially polysulfones, and for future re-lamination of polyarylates against polysulfones. or at least about 1 mil to reduce the number of recoatings. The laminates of the present invention can be prepared, for example, by solution coating with methylene chloride solution, by coextrusion of polyarylates with poly(arylethers), especially polysulfones, or by film coating with or without an adhesive interlayer. It can be manufactured by laminating sheets. Solution coating of polyarylates onto polysulfone surfaces using methylene chloride as the solvent for the polyarylates is a preferred method to achieve the desired layered structure. The coextrusion system of polyarylates and polysulfones is industrially attractive for solar energy applications, where the polysulfones provide a medium with good hydrolytic stability and the polyarylates are resistant to UV radiation exposure. Provides an effective UV radiation protection barrier to preserve the mechanical integrity of the system. As shown above, the laminate (laminate) of the present invention
is advantageously used in the utilization of solar energy, especially in solar heaters. The solar heater converts the projected solar radiation into thermal energy and transfers the absorbed heat to either a gas such as air or a liquid such as water. The former is usually called a solar air heater, and the latter is usually called a solar water heater. A typical solar heater includes at least a housing having a translucent or transparent front wall and a radiation-absorbing housing disposed within the housing and arranged to receive incident solar radiation passing through the front wall. It includes a collector element and means for passing the liquid or gaseous medium to be heated through the housing in heat transfer relationship with the collector element. The radiation-absorbing collector element is preferably constructed with a laminate of the invention, in which a polyarylate is exposed to incident solar radiation passing through the front wall, and a poly(aryl ether) is exposed to incident solar radiation passing through the front wall. , in particular polysulfone, is exposed to and forms a heat transfer relationship with means for passing the liquid or gaseous medium to be heated through the housing. Other possible uses of solar energy include, for example, the use of the laminates of the invention in the construction of solar heater housings, solar heater structural and support components, insulation and piping. Although the invention has been described with reference to numerous details, the invention is not limited thereto. The following examples are merely illustrative of embodiments of the invention as defined to date;
It is not intended to limit the scope or spirit of the invention in any way. Sheets used in Examples and Control Examples,
The film and coating solution are as follows: The numerical values and data are converted as follows. Foot = 30.48 cm Inch = 1 foot x 1/12 = 2.54 cm 1 mil = 1 inch x 1/1000 = 0.00254 cm Pound = 453 g Polyarylates Bisphenol A, terephthalic chloride and isophthalic chloride A transparent extruded polyarylate film having a thickness of 2 mils and manufactured by the Union Carbide Corporation under the designation Arder D-100 and sold by Union Carbide Corporation, USA under the designation Arder D-100. . Polyarylates prepared by conventional methods from bisphenol A and a mixture of 50 mol % each of terephthalic chloride and isophthalic chloride, and are made from union carbide.
A clear extruded polyarylate film having a thickness of 5 mils sold by Corporation Corporation under the designation Ardell D-100. Polyarylates prepared by conventional methods from bisphenol A and a mixture of 50 mol % each of terephthalic chloride and isophthalic chloride, and are made from union carbide.
A polyarylate solution consisting of about 12% by weight polyarylate in methylene chloride sold by Corporation Corporation under the designation Ardel D-100. Polymethyl methacrylate A cast polymethyl methacrylate transparent sheet having a thickness of 95 mils and sold under the designation Plexyglas by Rohm and Haas, USA. Polycarbonate A bright transparent polycarbonate sheet having a thickness of 128 mils and commercially available from General Electric Corporation under the symbol Lexan. Polyester Glass fiber reinforced polyester sheet having a thickness of 40 mils and formulated for outdoor use, sold under the symbol Kalwall by Kalwall Corporation, USA. Polyvinyl Fluoride A transparent polyvinyl fluoride film having a thickness of 4 mils and commercially available from DuPont, USA under the symbol Tedler. Glass Commercially available standard sheet glass having a thickness of 1/8 inch. The polysulfone substrates used in the examples and controls are as follows: Polysulfone in chloroform (0.2 g of polysulfone in 100 ml of chloroform at 25° C.)
It has a reduced viscosity of 0.49 measured in the following formula: A thermoplastic material with Analytical methods used in Examples and Control Examples
The ASTM standards are as follows: ASTM D-1925: Yellowness Index
Index) ASTM D-1003: Haze and light transmittance ASTM D-791: Purity. Color coefficient
Factor) is a value calculated from purity divided by thickness. Pendulum impact strength was measured as follows. Namely: A cylindrical shaped steel pendulum having a diameter of 0.85 inches and a height of 1.562 pounds was used. The shock strip, placed almost at the top of the pendulum, was a 0.3 inch diameter cylinder. Film specimens 4 inches long, 0.125 inches wide, and about 1 to 20 mils thick were sandwiched between the jaws of the tester with the jaws spaced 1 inch apart. The 0.125 inch width of the film was placed vertically. Place the pendulum on the specimen.
Raised to a constant height to give 1.13 foot pounds. When the pendulum was released, the cylindrical impact piece struck the coupon at its flat end, breaking the film and advancing the measured height distance. The difference in height regained (ie, the difference in positional energy of the pendulum at the highest point of upward swing) indicates the energy absorbed by the specimen during fracture. Dividing the pendulum energy loss by the volume of the specimen gives the impact strength in foot pounds per cubic inch. Examples 1 and 2 and Comparative Examples A-F The polysulfones described above were compression molded into platelets at 250° C. in a 4 inch x 0.020 inch cavity mold. Various films or sheets, also described above, were placed on the polysulfone platelets. The resulting laminates, as listed in the table below, were prepared using the procedures and equipment described in ASTM D-1499, with each of the above laminates placed on the polysulfone platelets with the exposed surface being a film or sheet. The specimens were subjected to accelerated weathering tests by placing them in an artificial exposure apparatus. After various exposure time intervals i.e. 200 hours, 400 hours, 500 hours, 600 hours
After 1000 hours and 1000 hours, the laminate was removed from each polysulfone platelet, the polysulfone platelets were sheared into 0.125 inch wide strips, and pendulum impact strength was measured on each polysulfone strip. The results of pendulum impact tests for various exposure time intervals are shown in the table. The initial pendulum impact strength of the polysulfone before exposure and the percent retention of the initial pendulum impact strength for each strip of polysulfone after various exposure time intervals are also shown in the table. Horizontal line symbols indicate that data were not available.

[Table] Acrylate

【table】
The results in the table demonstrate the protective properties of polyarylate films from the deleterious effects of long-term exposure, including exposure to ultraviolet radiation, even significantly superior to even significantly thicker sheets of other transparent coatings. Control example using only polysulfone, i.e. Control example A
shows significant discoloration (yellow) and develops severe haze after exposure. When polysulfone was coated with polyarylate films, namely polyarylate and polyarylate in Examples 1 and 2, respectively, the color (yellow) and haze of the polysulfone remained virtually unchanged after exposure. Examples 3-6 and Control Example G Five samples of polysulfone were compression molded into platelets at 250°C using a mold with a 4 inch x 4 inch x 0.020 inch cavity. Two polysulfone samples were then coated with polyarylate films as described above, i.e., Examples 3 and 4, and two other polysulfone samples were coated with polyarylate films also described above, i.e., Examples 5 and 6. solution coated with a polyarylate solution. The dry polyarylate films resulting from the solution coating had a thickness of 1.5 mils in Examples 5 and 6.
The remaining sample consisted only of polysulfone, ie, Control Example G, and was used as a control. The resulting laminates, listed in the table below, meet ASTM D-1499
Each laminate was subjected to an accelerated weathering test by placing it in an artificial exposure apparatus, with the film or coating on the polysulfone sample as the exposed surface, according to the procedure and apparatus described in .
The laminates were removed from the exposure apparatus after various exposure time intervals, namely 200 hours, 500 hours and 1000 hours, and the color coefficient, light transmittance, haze and purity were determined for each sample of sulfone.
The results of the color coefficient, light transmittance, haze and purity tests over various exposure time intervals are shown in the table.
The post-exposure light transmittance and haze values for Examples 3 and 4 were measured for 500 and 1000 hours of exposure on the polysulfone platelets alone, with the polyarylate film removed from the platelets (all The laminate (laminate) has initial data and
(used for 200 hours of data). Initial color coefficient, light transmittance, of polysulfone before exposure
Haze and purity are also shown in the table.

【table】

TABLE The results in the table demonstrate that even coatings as thin as, for example, 1.5 mils in thickness provide desirable protection from the adverse effects of long-term exposure, including exposure to ultraviolet radiation, as evidenced in Examples 5 and 6. The effects of the polyarylate films and coatings on polysulfone substrates are clearly demonstrated. The polysulfone control, Control G, shows a large increase in color index and haze and a decrease in light transmission after exposure. When polysulfone was coated with polyarylate films in Examples 3 and 4, i.e., polyarylate and polyarylate, respectively, the color coefficient, light transmittance, haze and purity were significantly less affected after exposure. shown. Similar results are observed for the solution coated laminates of Examples 5 and 6. The light transmittance and haze data were determined for the polysulfone and polyarylate film composite samples in Examples 3 and 4 for the initial values and the values listed for the 200 hour exposure. Therefore, the light transmittance and haze values are not as good as the polysulfone solution coated polyarylates of Examples 5 and 6 due to the air interlayer and two new surfaces in the composite sample. Control Examples H-M Samples of the polysulfone/polyarylate mixtures listed in the table below were tested at 250°C for 4 inches x 4 inches x 0.020 inches and 4 inches x 4.
Extrusion molding and compression molding were performed using molds with each cavity measuring 0.125 inch by 0.125 inch. The obtained platelets are
Each platelet was subjected to an accelerated exposure test by placing it in an artificial exposure apparatus according to the procedures and equipment described in ASTM D-1499. After 500 hours of exposure,
Plates for two sample sizes were removed from the exposure apparatus. Color index, yellowness index, and purity were measured for each polysulfone/polyarylate mixture molded in a 4 inch x 4 inch x 0.125 inch cavity mold. Pendulum impact strength was measured for each polysulfone/polyarylate mixture compression molded in a 4 inch x 4 inch x 0.020 inch cavity mold. The color coefficient, yellowness index, purity and pendulum impact strength test results after 500 hours of exposure are shown in the table. Initial color coefficient of polysulfone/polyarylate platelets before exposure,
The yellow index and pendulum impact strength are also shown in the table.

[Table] Polyary rate
(25% by weight)
Control Examples HM clearly illustrate that polysulfones and polyarylates, namely polysulfones and polyarylates, are unstable when subjected to exposure to ultraviolet radiation. Polyarylates are ineffective UV radiation stabilizers when mixed with polysulfones. However, poly(aryl ethers), particularly polyarylates laminated as laminates onto polysulfones, exhibit excellent protection against degradation of the polysulfones after exposure to long-term UV radiation.

Claims (1)

[Claims] 1. A polyarylate derived from a dihydric phenol and an aromatic dicarboxylic acid or a mixture thereof with the formula: (-O-E-O-E')- (wherein E is secondary E' is a residue of a divalent phenol, and E' is a residue of a dihalobenzenoid compound having an inert electron-withdrawing group at at least one position ortho and para to the valence bond. A laminate formed by laminating on the surface of a poly(aryl ether) having a repeating unit in which both of the above-mentioned residues are valently bonded to the ether oxygen via an aromatic carbon atom. 2 Divalent phenol has the formula: (wherein Y is selected from an alkyl group having 1 to 4 carbon atoms, chlorine or bromine, z independently has a value of 0 to 4, and R' is an alkylene group having 1 to 3 carbon atoms. and alkylidene groups, and divalent, saturated or unsaturated aliphatic hydrocarbon groups selected from cycloalkylene groups and cycloalkylidene groups having up to 9 carbon atoms. 1st
Laminated body as described in section. 3. The laminate according to claim 2, wherein each z is 0 and R' is an alkylidene group having 3 carbon atoms. 4. The laminate according to claim 1, wherein the divalent phenol is hydroquinone. 5. The laminate according to claim 1, wherein the divalent phenol is resorcinol. 6. The laminate according to claim 1, wherein the aromatic dicarboxylic acid is selected from terephthalic acid, isophthalic acid, or a mixture thereof. 7. Claim 1 in which the polyarylate is derived from bisphere A and a mixture of 50 mol% each of terephthalic acid and isophthalic acid.
Laminated body as described in section. 8. A laminate according to claim 1, wherein the polyarylate is derived from hydroquinone and a mixture of 50 mol % each of terephthalic acid and isophthalic acid. 9 Poly(aryl ether) has the formula: The laminate according to claim 8, having a repeating unit of. 10 Poly(aryl ether) has the formula: The laminate according to claim 1, having a repeating unit of. 11 Polyary rate is at least 0.00254cm
The laminate according to claim 1, having a layer thickness of .